CN112108020B - Polyamide nanofiltration membrane and preparation method and application thereof - Google Patents
Polyamide nanofiltration membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a polyamide nanofiltration membrane as well as a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) activating the polyamide-based membrane by using an activating agent to obtain an activated polyamide-based membrane; (2) and (2) grafting the activated polyamide base membrane obtained in the step (1) by using an amino compound to obtain the polyamide nanofiltration membrane. The preparation method has the advantages of simple process, convenient operation and the like; on one hand, the prepared polyamide nanofiltration membrane has the advantages of small surface macropore number, small average pore diameter and high retention rate on small organic molecules; on the other hand, the electronegativity is low, and the rejection rate of monovalent inorganic salt is low; the polyamide nanofiltration membrane also has excellent alkali-resistant swelling property and chemical stability, and has wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of separation membranes, and particularly relates to a polyamide nanofiltration membrane as well as a preparation method and application thereof.
Background
The polyamide nanofiltration membrane has the advantages of simple preparation process, small aperture, high water permeation flux, strong pollution resistance and the like, so that the polyamide nanofiltration membrane becomes the most successful nanofiltration membrane for industrial application at present, and is widely applied to the fields of drinking water treatment, wastewater reclamation, biological product decolorization, micromolecule desalination and the like. M-phenylenediamine or piperazine and trimesoyl chloride monomers are subjected to rapid polymerization at an oil-water two-phase interface to form an ultrathin polyamide separation layer with the thickness of less than one micron on a polysulfone ultrafiltration membrane substrate so as to form a polyamide nanofiltration membrane, but residual acyl chloride groups on the surface of the separation layer can be hydrolyzed into carboxyl groups in the washing stage or the using process of the membrane, so that the crosslinking degree of the surface of the membrane and the pore size distribution of the separation layer are uneven, and the retention rate of organic micromolecules is reduced; meanwhile, the surface film surface of the polyamide nanofiltration membrane has higher electronegativity, and the rejection rate of inorganic salt is increased; therefore, it is not effective in separating organic small molecules having a molecular weight of less than 300Da from monovalent salts.
The nanofiltration membrane is modified by a common means for improving the separation selectivity, and most of the prior nanofiltration membrane modification technologies focus on surface charge regulation and control of the nanofiltration membrane so as to improve the rejection rate of the nanofiltration membrane on inorganic salts. CN109692585A discloses a nanofiltration membrane surface modification method, wherein a polypiperazine amide separation layer of a nanofiltration membrane reacts with an ammonium salt containing an epoxy group, so that the epoxy group in the ammonium salt containing the epoxy group is covalently connected with an amino group on the membrane surface, the hydrophilicity and the positive charge of the nanofiltration membrane are improved, and the rejection rate of the nanofiltration membrane on divalent cations is increased. However, the effect of the modified nanofiltration membrane on separating organic small molecules with the molecular weight of less than 300Da from monovalent salt still needs to be improved. CN110026091A discloses a preparation method of an ionic liquid modified positively charged nanofiltration membrane, wherein the positively charged nanofiltration membrane is prepared by amidation reaction of residual acyl chloride groups on the surface of a nascent polyamide layer and amino functionalized ionic liquid, and the obtained positively charged nanofiltration membrane can be used for magnesium-lithium separation in salt lake brine, has the advantages of simple preparation method, low cost and the like, and has good industrial application prospect in the aspect of lithium extraction in salt lakes. CN110052179A discloses a preparation method of an anti-pollution composite nanofiltration membrane, the anti-pollution nanofiltration membrane is prepared by covalently connecting a nonionic hydrophilic base polymer containing ether bonds in a main chain with residual acyl chloride groups on the surface of a nascent polyamide nanofiltration membrane, the surface of the modified nanofiltration membrane is smooth, the roughness is reduced, the number of residual carboxyl groups on the surface is reduced, and the anti-pollution performance and the retention rate of organic micromolecules of the nanofiltration membrane are greatly improved. The two nanofiltration membrane modification methods improve the separation efficiency of the nanofiltration membrane by changing the surface charge or hydrophilicity of the membrane, but the modified polyamide nanofiltration membrane still swells in an alkaline environment with the pH value of more than 11, the retention rate of organic micromolecules after alkali cleaning is remarkably reduced, and meanwhile micromolecular pollutants are easy to enter the pores of the nanofiltration membrane to form irreversible pollution.
Therefore, the polyamide nanofiltration membrane with alkali-resistant swelling performance and chemical cleaning stability is developed, is used for improving the separation selectivity of small organic molecules and monovalent inorganic salts, and has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyamide nanofiltration membrane and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a polyamide nanofiltration membrane, which comprises the following steps:
(1) activating the polyamide-based membrane by using an activating agent to obtain an activated polyamide-based membrane;
(2) and (2) grafting the activated polyamide base membrane obtained in the step (1) by using an amino compound to obtain the polyamide nanofiltration membrane.
The invention provides a preparation method of a polyamide nanofiltration membrane, which comprises the following specific steps of: wherein, 1 represents a polyamide-based membrane, 2 represents an activated polyamide-based membrane, and 3 represents a polyamide nanofiltration membrane; firstly, carboxyl on a polyamide base membrane 1 is specifically activated by an activating agent to obtain an activated polyamide base membrane 2, and then an amino compound is grafted to finally obtain the polyamide nanofiltration membrane 3. The whole preparation process is simple in process and convenient to operate; the prepared polyamide nanofiltration membrane has excellent alkali-resistant swelling performance and chemical cleaning stability, and is beneficial to improving the separation selectivity of small organic molecules and monovalent inorganic salts.
Preferably, the polyamide-based film comprises a support film, and a polyamide layer disposed on a surface of the support film.
Preferably, the polyamide-based film has a molecular weight cut-off of 100 to 500Da, such as 120Da, 140Da, 160Da, 180Da, 200Da, 220Da, 240Da, 260Da, 280Da, 300Da, 320Da, 340Da, 360Da, 380Da, 400Da, 420Da, 440Da, 460Da, or 480Da, and specific values therebetween, not to be limited in space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the ranges.
Preferably, the support membrane comprises any one of or a combination of at least two of a polyethersulfone ultrafiltration membrane, a polysulfone ultrafiltration membrane, or a polyethylene microfiltration membrane.
Preferably, the polyamide layer is prepared by interfacial polymerization of polyamine and trimesoyl chloride.
Preferably, the polyamine comprises m-phenylenediamine and/or piperazine.
Preferably, the activating agent of step (1) comprises a combination of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide.
As a preferred technical scheme, the combination of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) is selected as an activating agent, so that an activated polyamide-based membrane can be obtained, and a polyamide nanofiltration membrane with excellent performance can be further obtained; the schematic diagram of the preparation process of the polyamide nanofiltration membrane by using EDC and NHS as activators is shown in FIG. 2, and the step I is a process of activating carboxyl on a polyamide-based membrane by EDC; step two, combining NHS and the product after EDC activation to generate an activated polyamide-based membrane; step three is the process of grafting amino compound and activated polyamide base membrane to obtain the polyamide nanofiltration membrane, wherein R3-NH2Represents an amino compound.
Preferably, the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the N-hydroxysuccinimide is 1: (1 to 3) include, for example, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9 and the like, and more preferably 1 (1.5 to 1.7).
Preferably, the activating agent of step (1) is dissolved in 2- (N-morpholino) ethanesulfonic acid buffer.
Preferably, the pH of the 2- (N-morpholine) ethanesulfonic acid buffer solution is 3 to 6, such as 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8 or 4.9, and the specific values therebetween are not intended to be exhaustive and for brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the pH value of the 2- (N-morpholine) ethanesulfonic acid buffer solution is 5-6.
Preferably, the mass of the EDC is 0.2-1 g, such as 0.25g, 0.3g, 0.35g, 0.4g, 0.45g, 0.5g, 0.55g, 0.6g, 0.65g, 0.7g, 0.75g, 0.8g, 0.85g, 0.9g or 0.95g based on 1L of the 2- (N-morpholine) ethanesulfonic acid buffer solution, and specific points therebetween, including space and brevity, the invention is not exhaustive and does not include specific points included in the range.
Preferably, the mass of the EDC is 0.4-0.6 g based on 1L of the 2- (N-morpholine) ethanesulfonic acid buffer solution.
Preferably, the activation time in step (1) is 0.5-5 h, such as 0.7h, 0.9h, 1.1h, 1.3h, 1.5h, 1.7h, 1.9h, 2.1h, 2.3h, 2.5h, 2.7h, 2.9h, 3.1h, 3.3h, 3.5h, 3.7h, 3.9h, 4.1h, 4.3h, 4.5h, 4.7h or 4.9h, and the specific values therebetween are not exhaustive and for the sake of brevity, and the invention is not exhaustive.
Preferably, the activation time of the step (1) is 0.8-1.2 h.
Preferably, the temperature of the activation in step (1) is 25-50 ℃, such as 27 ℃, 29 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃, 41 ℃, 43 ℃, 45 ℃, 47 ℃ or 49 ℃, and the specific values therebetween are limited by the space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the temperature for activating in the step (1) is 30-40 ℃.
In the invention, the polyamide-based film in the step (1) is a polyamide-based film treated by an alkaline aqueous solution.
As a preferable technical scheme of the invention, the polyamide base membrane is a polyamide base membrane treated by an alkaline aqueous solution, and an amide group on the base membrane treated by the alkaline aqueous solution is hydrolyzed into a carboxyl group, so that more activation sites are provided for activation of an activating agent, subsequent grafting of an amino compound is facilitated, and the polyamide nanofiltration membrane with high separation selectivity and excellent separation effect is further prepared.
Preferably, the pH of the aqueous alkaline solution is 10 to 11.5, such as 10.2, 10.4, 10.6, 10.8, 11, 11.2 or 11.4, and the specific values therebetween are not exhaustive for the sake of brevity and clarity.
Preferably, the pH value of the alkaline aqueous solution is 10.8-11.2.
Preferably, the time for the alkaline aqueous solution treatment is 0.5-3 h, 0.7h, 0.9h, 1.1h, 1.3h, 1.5h, 1.7h, 1.9h, 2.1h, 2.3h, 2.5h, 2.7h or 2.9h, and the specific values therebetween are limited by space and for the sake of brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the time for treating the alkaline aqueous solution is 0.8-1.2 h.
Preferably, the temperature of the alkaline aqueous solution treatment is 25 to 35 ℃, for example, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃ or 34 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the temperature of the alkaline aqueous solution treatment is 28-32 ℃.
Preferably, the amino compound in step (2) comprises any one of n-propanolamine, 1, 3-propanediamine, glucosamine, polyethyleneimine, polyacrylamide, polyglutamic acid or chitosan or a combination of at least two thereof.
Preferably, the amino compound has a molecular weight of 75-10000 Da, such as 100Da, 200Da, 400Da, 600Da, 800Da, 1000Da, 1200Da, 1600Da, 1800Da, 2000Da, 2200Da, 2500Da, 2700Da, 3000Da, 3500Da, 4000Da, 4500Da, 5000Da, 6000Da, 7000Da, 7500Da, 8000Da, 9000Da or 9500Da, and specific point values therebetween, limited in space and for brevity, the invention is not exhaustive of the specific point values included in the range, and more preferably 500-2000 Da.
Preferably, the grafting time in step (2) is 1 to 4 hours, such as 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours or 3.8 hours, and specific values therebetween, which are limited by space and for the sake of brevity, are not exhaustive, and the invention does not include the specific values included in the range.
Preferably, the grafting time of step (2) is 2 h.
Preferably, the temperature of the grafting in the step (2) is 25-50 ℃, for example, 27 ℃, 29 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃, 39 ℃, 41 ℃, 43 ℃, 45 ℃, 47 ℃ or 49 ℃, and the specific values therebetween are limited by the space and the conciseness, and the invention is not exhaustive list of the specific values included in the range.
Preferably, the temperature of grafting in the step (2) is 35-40 ℃.
Preferably, the amino compound of step (2) is dissolved in a phosphate buffer.
Preferably, the pH of the phosphate buffer is 4-7, such as 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.2, 6.4, 6.6, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the pH value of the phosphate buffer is 5.5-6.5.
Preferably, the mass of the amino compound is 0.2-1 g, such as 0.3g, 0.4g, 0.5g, 0.6g, 0.7g, 0.8g or 0.9g, based on 1L of the phosphate buffer solution, and the specific values therebetween are not exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the mass of the amino compound is 0.2-0.6 g based on 1L of the phosphate buffer solution.
Preferably, the preparation method specifically comprises the following steps:
(1) placing the polyamide-based film in an alkaline aqueous solution with the pH value of 10-11.5, and treating for 0.5-3 h at 25-35 ℃ to obtain a pretreated polyamide-based film; activating the pretreated polyamide base film by using an activating agent at the temperature of 25-50 ℃ for 0.5-5 h to obtain an activated polyamide base film; the activating agent is EDC and NHS;
(2) and (2) grafting the activated polyamide base membrane obtained in the step (1) for 1-4 h at 25-50 ℃ by using an amino compound to obtain the polyamide nanofiltration membrane, wherein the amino compound comprises any one or a combination of at least two of n-propanolamine, 1, 3-propanediamine, glucosamine, polyethyleneimine, polyacrylamide, polyglutamic acid and chitosan.
In a second aspect, the invention provides a polyamide nanofiltration membrane prepared by the preparation method of the first aspect.
In a third aspect, the invention provides the use of a polyamide nanofiltration membrane as described in the second aspect for separating reducing sugars from monovalent inorganic salts.
Preferably, the reducing sugar comprises glucose and/or fructose.
Preferably, the monovalent salt comprises potassium chloride and/or sodium chloride.
Compared with the prior art, the invention has the following beneficial effects:
in the preparation method of the polyamide nanofiltration membrane, the polyamide nanofiltration membrane is obtained by performing activation treatment on the polyamide base membrane, grafting an amino compound and the like, and the preparation method is simple in process and convenient to operate; the prepared polyamide nanofiltration membrane has the advantages of small surface macropore number, small average pore diameter and high retention rate on small organic molecules; the electronegativity is low, the retention rate of inorganic salt is low, and the alkali-resistant swelling property and the chemical stability are excellent. The separation factor of the polyamide nanofiltration membrane prepared by the preparation method for glucose and potassium chloride is 2.5-4.4, which is increased by 56-175% compared with the separation factor of glucose and potassium chloride by using the polyamide nanofiltration membrane in the prior art; in general, the selectivity of selective separation of small organic molecules and monovalent inorganic salts can be improved by 20-100%, and the method has a good application prospect.
Drawings
FIG. 1 is a schematic diagram of the specific steps of the preparation method provided by the present invention;
figure 2 is a schematic diagram of a preparation process for preparing a polyamide nanofiltration membrane by using EDC and NHS as activators.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of a polyamide nanofiltration membrane comprises the following specific steps:
(1) the molecular weight cut-off of XN45 (Trisep) with the molecular weight of 300DaTM) Placing the polyamide basement membrane in a sodium hydroxide aqueous solution with the pH value of 11, treating for 1h at 30 ℃, and cleaning to obtain a pretreated polyamide basement membrane;
(2) treating the pretreated polyamide-based membrane obtained in step (1) in MES buffer (0.1M, pH 5) containing EDC and NHS at 37 deg.C for 1 h; wherein the mass concentration of EDC in the MES buffer solution is 0.5g/L, and the mass concentration of NHS is 0.8g/L, so as to obtain an activated polyamide-based membrane;
(3) and (3) treating the activated polyamide-based membrane obtained in the step (2) in Phosphate Buffer (PBS) with molecular weight of 1800Da polyethyleneimine (0.1M, pH value is 6) at 37 ℃ for 1h, wherein the mass concentration of the polyethyleneimine in the PBS buffer is 0.4g/L, so as to obtain the polyamide nanofiltration membrane.
Example 2
A preparation method of a polyamide nanofiltration membrane comprises the following specific steps:
(1) placing the NF270 polyamide-based membrane with the molecular weight cutoff of 200Da in a sodium hydroxide aqueous solution with the pH value of 11.5, treating for 1h at 25 ℃, and cleaning to obtain a pretreated polyamide-based membrane;
(2) treating the pretreated polyamide-based membrane obtained in step (1) in MES buffer (0.1M, pH 5) containing EDC and NHS at 37 deg.C for 1 h; wherein the mass concentration of EDC in the MES buffer solution is 0.4g/L, and the mass concentration of NHS is 0.6g/L, so as to obtain an activated polyamide-based membrane;
(3) and (3) treating the activated polyamide-based membrane obtained in the step (2) in Phosphate Buffer (PBS) with molecular weight of 600Da polyethyleneimine (0.1M, pH is 6) at 37 ℃ for 2h, wherein the mass concentration of the polyethyleneimine in the PBS buffer is 0.3g/L, so as to obtain the polyamide nanofiltration membrane.
Example 3
A preparation method of a polyamide nanofiltration membrane comprises the following specific steps:
(1) placing XN45 polyamide-based membrane with molecular weight cutoff of 300Da in sodium hydroxide aqueous solution with pH value of 10.5, treating at 35 deg.C for 1h, and cleaning to obtain pretreated polyamide-based membrane;
(2) treating the pretreated polyamide-based membrane obtained in step (1) in MES buffer (0.1M, pH 5) containing EDC and NHS at 37 deg.C for 2 h; wherein the mass concentration of EDC in the MES buffer solution is 0.5g/L, and the mass concentration of NHS is 0.8g/L, so as to obtain an activated polyamide-based membrane;
(3) and (3) treating the activated polyamide-based membrane obtained in the step (2) in Phosphate Buffer (PBS) of chitosan (0.1M, pH is 6) at 37 ℃ for 2h, wherein the mass concentration of chitosan in the PBS buffer is 0.3g/L, so as to obtain the polyamide nanofiltration membrane.
Example 4
The preparation method of the polyamide nanofiltration membrane is different from the preparation method of the embodiment 1 only in that the polyamide base membrane is directly subjected to the step (2) without the step (1), and the amounts of other components and experimental conditions are the same as those of the embodiment 1, so that the polyamide nanofiltration membrane is obtained.
Example 5
A method for preparing a polyamide nanofiltration membrane, which is different from the method in example 1 only in that MES buffer solution of EDC and NHS in the step (2) is replaced by MES buffer solution (0.1M, pH 5) with EDC of 1.3g/L in mass concentration, and the amounts of other components and experimental conditions are the same as those in example 1, so as to obtain the polyamide nanofiltration membrane.
Example 6
A method for preparing a polyamide nanofiltration membrane, which is different from the method in example 1 only in that MES buffer solution of EDC and NHS in the step (2) is replaced by MES buffer solution of NHS with the mass concentration of 1.3g/L (0.1M, pH 5), and the amounts of other components and experimental conditions are the same as those in example 1, so as to obtain the polyamide nanofiltration membrane.
Comparative example 1
The preparation method of the polyamide nanofiltration membrane is different from that of example 1 in that the pretreated polyamide-based membrane obtained in step (1) is directly subjected to step (3) without being subjected to step (2), and the amounts of other components and experimental conditions are the same as those of example 1, so that the polyamide nanofiltration membrane is obtained.
Comparative example 2
The preparation method of the polyamide nanofiltration membrane is different from that of example 1 in that the activated polyamide base membrane obtained in the step (2) does not pass through the step (3), and the amounts of other components and experimental conditions are the same as those of example 1, so that the polyamide nanofiltration membrane is obtained.
Comparative example 3
A preparation method of a polyamide nanofiltration membrane directly uses an XN45 polyamide-based membrane with the molecular weight cutoff of 300Da as the polyamide nanofiltration membrane.
Comparative example 4
A preparation method of a polyamide nanofiltration membrane directly uses a NF270 polyamide-based membrane with the molecular weight cutoff of 200Da as the polyamide nanofiltration membrane.
Application examples 1 to 6
A separation method of a mixed aqueous solution of glucose and potassium chloride comprises the following specific steps:
the polyamide nanofiltration membrane obtained in the embodiment 1 to 6 is matched with a constant-flux dead-end filtering device to separate the mixed aqueous solution of glucose and potassium chloride, so that the aqueous solution of potassium chloride and the aqueous solution of glucose can be obtained. Wherein the mass concentration of potassium chloride in the mixed aqueous solution is 5g/L, and the mass concentration of glucose is 4 g/L.
And (3) performance testing:
adopting a constant-flux dead-end filtering device, injecting 13mL of mixed aqueous solution of glucose and potassium chloride into a filtering device with an effective filtering area of 4.52 multiplied by 10-4m2The temperature of the membrane filtration device was kept constant at 25 ℃ while keeping the rotation speed at 1200rpm in the magnetically stirred dead-end filter of (1), wherein the mass concentration of potassium chloride in the mixed aqueous solution was 5g/L and the mass concentration of glucose was 4 g/L.
(1) Pure water permeability coefficient: at constant flux of 53.1 L.m-2·h-1And continuously pumping deionized water into a filter of the constant-flux dead-end filtering device (percolation mode) under the condition, collecting trapped fluid, stopping filtering after 13mL of permeate is obtained, and dividing the volume of the permeate by the area, filtering time and average transmembrane pressure of the nanofiltration membrane to obtain the pure water permeability coefficient.
(2) Retention and separation factor: in the diafiltration mode, 13mL of mixed aqueous solution of glucose and potassium chloride was injected into the filter of the constant flux dead-end filtration unit, wherein the mass concentration of potassium chloride in the mixed aqueous solution was 5g/L and the mass concentration of glucose was 4g/L, and then 53.1L · m-2·h-1Pumping 13mL of pure water into the filter by the flux, and stopping filtering; and collecting the permeation solution and the trapped solution, and respectively calculating according to a formula I and a formula II to obtain the apparent trapping rates (Robs) and the Separation factor (Separation factor) of the glucose and the potassium chloride.
In the formula I, Cp、CrAnd CfThe concentrations of glucose or potassium chloride in the permeate, retentate and the original mixed aqueous solution are expressed in g/L, respectively.
In the formula II, wherein RsRetention rate of potassium chloride，RbThe retention rate of glucose is shown.
The polyamide nanofiltration membranes obtained by the preparation methods provided in examples 1 to 6 and comparative examples 1 to 4 were tested according to the test methods, and the test results are shown in table 1:
TABLE 1
The data in table 1 show that the polyamide nanofiltration membrane prepared by the preparation method provided by the invention has greatly improved separation selectivity under the condition of ensuring little reduction of water flux. Specifically, the separation factor of the polyamide nanofiltration membrane obtained in the embodiments 1 and 3 to 6 is 2.5 to 4.4, which is increased by 56 to 175% compared with the polyamide nanofiltration membrane obtained in the comparative example 3; the separation factor of the polyamide nanofiltration membrane obtained in example 2 is 5.4, and compared with the polyamide nanofiltration membrane obtained in comparative example 4, the separation factor is increased by 145%, which shows that the polyamide nanofiltration membrane provided by the method has higher separation selectivity for potassium chloride and glucose.
Further, by comparing example 1 with example 4, it can be found that the polyamide nanofiltration membrane obtained in example 1 has a higher separation factor, which indicates that the polyamide nanofiltration membrane has a higher separation selectivity for potassium chloride and glucose, and proves that the polyamide basement membrane is pretreated with an alkaline aqueous solution before activation to carboxylate the surface of the polyamide basement membrane, so that the selective separation selectivity of the finally prepared polyamide nanofiltration membrane is improved; comparing example 1 with examples 5 and 6, it can be seen that the polyamide nanofiltration membrane obtained in example 1 has a higher separation factor, which indicates that the polyamide nanofiltration membrane has a higher selective separation selectivity for potassium chloride and glucose, and it is proved that when the activating agent is a combination of EDC and NHS, the activation of the polyamide-based membrane and the further grafting of the amino compound are facilitated, and the obtained polyamide nanofiltration membrane has a higher separation selectivity.
Meanwhile, the invention also limits two steps of activation and grafting, can effectively improve the separation selectivity of the prepared polyamide nanofiltration membrane on organic micromolecules and monovalent inorganic salts, and if the polyamide nanofiltration membrane prepared without the step of activation (comparative example 1) or the step of grafting amino compounds (comparative example 2) has little improvement on the separation factor, the polyamide nanofiltration membrane with high separation selectivity can not be obtained.
The applicant states that the invention is described by the above examples to illustrate a polyamide nanofiltration membrane and a preparation method and an application process thereof, but the invention is not limited to the above process steps, i.e. the invention does not depend on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (37)
1. A preparation method of a polyamide nanofiltration membrane for separating reducing sugar and monovalent inorganic salt, which is characterized by comprising the following steps:
(1) activating the polyamide-based membrane by using an activating agent to obtain an activated polyamide-based membrane;
(2) grafting the activated polyamide base membrane obtained in the step (1) by using an amino compound to obtain the polyamide nanofiltration membrane;
the molecular weight cutoff of the polyamide-based membrane in the step (1) is 100-500 Da;
the activating agent of step (1) comprises a combination of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide;
the mass ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the N-hydroxysuccinimide is 1: (1-3);
the molecular weight of the amino compound in the step (2) is 500-10000 Da.
2. The production method according to claim 1, wherein the polyamide-based film comprises a support film, and a polyamide layer provided on a surface of the support film.
3. The production method according to claim 2, wherein the support membrane comprises any one of a polyethersulfone ultrafiltration membrane, a polysulfone ultrafiltration membrane, or a polyethylene microfiltration membrane or a combination of at least two thereof.
4. The method according to claim 2, wherein the polyamide layer is prepared by interfacial polymerization of polyamine and trimesoyl chloride.
5. The method according to claim 4, wherein the polyamine comprises m-phenylenediamine and/or piperazine.
6. The method according to claim 1, wherein the mass ratio of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to N-hydroxysuccinimide is 1 (1.5-1.7).
7. The method of claim 1, wherein the activator of step (1) is dissolved in 2- (N-morpholine) ethanesulfonic acid buffer.
8. The method according to claim 7, wherein the pH of the 2- (N-morpholino) ethanesulfonic acid buffer solution is 3 to 6.
9. The method according to claim 8, wherein the pH of the 2- (N-morpholino) ethanesulfonic acid buffer solution is 5 to 6.
10. The method according to claim 7, wherein the mass of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 0.2-1 g, based on 1L of the 2- (N-morpholino) ethanesulfonic acid buffer solution.
11. The method according to claim 10, wherein the mass of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 0.4-0.6 g, based on 1L of the 2- (N-morpholino) ethanesulfonic acid buffer solution.
12. The preparation method according to claim 1, wherein the activation time in step (1) is 0.5-5 h.
13. The method according to claim 12, wherein the activation time in step (1) is 0.8-1.2 h.
14. The method according to claim 1, wherein the temperature for activating in step (1) is 25 to 50 ℃.
15. The method according to claim 14, wherein the temperature for activating in step (1) is 30 to 40 ℃.
16. The production method according to claim 1, wherein the polyamide-based film of step (1) is a polyamide-based film treated with an aqueous alkaline solution.
17. The method according to claim 16, wherein the pH of the aqueous alkaline solution is 10 to 11.5.
18. The method according to claim 17, wherein the pH of the aqueous alkaline solution is 10.8 to 11.2.
19. The method according to claim 16, wherein the time for treating with the alkaline aqueous solution is 0.5 to 3 hours.
20. The method according to claim 19, wherein the time for treating with the alkaline aqueous solution is 0.8 to 1.2 hours.
21. The method according to claim 16, wherein the temperature of the treatment with the alkaline aqueous solution is 25 to 35 ℃.
22. The method according to claim 21, wherein the temperature of the treatment with the alkaline aqueous solution is 28 to 32 ℃.
23. The method according to claim 1, wherein the amino compound in the step (2) comprises any one of glucosamine, polyethyleneimine, polyacrylamide, polyglutamic acid, or chitosan, or a combination of at least two thereof.
24. The preparation method according to claim 1, wherein the grafting time in the step (2) is 1-4 h.
25. The preparation method of claim 24, wherein the grafting time of step (2) is 1.8-2.2 h.
26. The method according to claim 1, wherein the temperature of the grafting in the step (2) is 25 to 50 ℃.
27. The method according to claim 26, wherein the temperature of the grafting in the step (2) is 35 to 40 ℃.
28. The method according to claim 1, wherein the amino compound in the step (2) is dissolved in a phosphate buffer.
29. The method according to claim 28, wherein the phosphate buffer has a pH of 4 to 7.
30. The method according to claim 29, wherein the phosphate buffer has a pH of 5.5 to 6.5.
31. The method according to claim 30, wherein the amino compound has a mass of 0.2 to 1g based on 1L of the phosphate buffer solution.
32. The method according to claim 31, wherein the amino compound has a mass of 0.2 to 0.6g based on 1L of the phosphate buffer solution.
33. The preparation method according to claim 1, characterized in that the preparation method comprises the following steps:
(1) placing the polyamide-based film in an alkaline aqueous solution with the pH value of 10-11.5, and treating for 0.5-3 h at 25-35 ℃ to obtain a pretreated polyamide-based film; activating the pretreated polyamide base film by using an activating agent at the temperature of 25-50 ℃ for 0.5-5 h to obtain an activated polyamide base film; the activating agent is a combination of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide;
(2) and (2) grafting the activated polyamide base membrane obtained in the step (1) for 1-4 h at 25-50 ℃ by using an amino compound to obtain the polyamide nanofiltration membrane, wherein the amino compound comprises any one or a combination of at least two of n-propanolamine, 1, 3-propanediamine, glucosamine, polyethyleneimine, polyacrylamide, polyglutamic acid and chitosan.
34. A polyamide nanofiltration membrane, wherein the polyamide nanofiltration membrane is prepared by the preparation method of any one of claims 1 to 33.
35. Use of a polyamide nanofiltration membrane according to claim 34 for separating reducing sugars and monovalent inorganic salts.
36. Use according to claim 35, wherein said reducing sugar comprises glucose and/or fructose.
37. The use of claim 35, wherein the monovalent inorganic salt comprises potassium chloride and/or sodium chloride.
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